[Ni(NN)(SS)]混配配合物的合成与性质

Four new complexes of the general formula [Ni(SS)(NN)], Where SSis dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate) or pddt(6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate) and NNis bpy or phen were prepared. The UV/Vis.Spectra exhibit intense intramolecular ligand-to-ligand charge transfer bands ca.600 nm.Cyclic voltammetry shows a reversible oxidation step assigned to [Ni(SS)(NN)]⁰=[Ni(SS)(NN)]⁺. When the complex [Ni(dddt)(bpy)] was partially oxidized by I₂, a broad ESRsignal at g=2.003 appeared.     

Synthesis,structures and magnetic properties of nickel bis (dithiolene) complexes with [Fe(qsal)2]+

Two new compounds containing the possible Fe(III) spin-crossover cation, [Fe(qsal)₂]⁺ (qsalH = N-(8-quinolyl)salicylaldimine), and nickel bis(dithiolene) anions have been synthesized. Both are 1 : 1 salts [Fe(qsal)₂][Ni(dddt)₂] · CH₃CN · CH₃OH (1) and [Fe(qsal)₂][Ni(pddt)₂] (2) (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate; pddt = 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate). They have been characterized by X-ray crystal structure determination, elemental analysis, UV-Vis spectra and magnetic susceptibility measurements. The UV–Vis spectra are dominated by [Ni(L)₂]^? (1, L = dddt; 2, L = pddt). Magnetic studies show antiferromagnetic interaction in 1 from intermolecular S···S contacts and π–π stacking interactions, while the antiferromagnetic interaction in 2 is very weak.     

Coordination polymers and supramolecular structures in Ag(I)triflate-dppf systems (dppf=1,1-bis(diphenylphosphino)ferrocene)

The interaction of silver triflate (OTf⁻=SO₃(CF₃)⁻) and dppf [(C₅H₄PPh₂)₂Fe)] gave different complexes, depending on the stoichiometric proportions and reaction conditions. Under limiting dppf conditions, three different forms (1-3) of [Ag₂(OTf)₂(dppf)]_x were isolated. Single crystal X-ray diffraction analyses showed that the structure of 1 (x=2n) consists of a 2-D polymer comprising a tetra-silver basic unit, while that of 2 (x=2) possesses a discrete tetra-silver framework and that of 3 (x=n) is a linear polymer based on a di-silver repeating unit. The structures are supported by bridging dppf ligands and triflate groups. The crystal lattices of the compounds are stabilized by extensive intermolecular C-H?X hydrogen bonding (H=ring proton of Cp or Ph of dppf; X=O or F of OTf). [Ag(dppf)(OTf)] (4) and the structurally characterized mononuclear [Ag(dppf)₂](OTf) (5) were the sole products obtained from treatment of AgOTf with dppf in molar ratios of 1:1 and 1:2, respectively.     

Molecular Conductors Based on M(dddt)2 Bisdithiolene Cation Complexes

The synthesis, structure and properties of molecular conductors based on M(dddt)₂ cation complexes (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate) which are metal complex analogs of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) salts are considered. Formally, the central C=C bond of ET is substituted by a metal ion in the M(dddt)₂ complexes. The effect of metal (M=Ni, Pt, Pd) and counterion on crystal structure and conducting properties of M(dddt)₂ complexes is analyzed. The similarity and distinction in structures and properties of M(dddt)₂ and ET salts are discussed.     

An Examination of the Coordination Chemistry of L2Pt(1,2-DITHIOLENES) Using Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

Atmospheric pressure chemical ionization mass spectrometry (APCI–MS) has been utilized in the characterization of two series of platinum dithiolene complexes, (COD)Pt(dt) 1, (COD)–Pt(edt) 2, (COD)Pt(dmid) 3, (COD)Pt(mnt) 4, (COD)Pt(eddo) 5, (COD)Pt(dddt) 6 and (Ph₃P)₂Pt(dt) 7, (Ph₃P)₂Pt(edt) 8, (Ph₃P)₂Pt(dmid) 9, (Ph₃P)₂Pt(dmit) 10, (Ph₃P)₂Pt(mnt) 11 (where COD = 1,5–cyclooctadiene, dt = ethane–1,2–dithiolate, edt = ethylene–1,2–dithiolate, dmid = 1,3–dithiole–2–oxo–4,5–dithiolate, dmit = 1,3–dithiole–2–thione–4,5–dithiolate, mnt = maleonitrile–1,2–dithiolate, eddo = 4–(ethylene–1′,2′–dithiolate)–1,3-dithiole–2–one, and dddt = 5,6–dihydro–1,4–dithiin–2,3–dithiolate). The series that contains triphenylphosphine is labile toward the loss of HPPh₃ ⁺. In addition, an orthometallated species involving the platinum and triphenylphosphine is identified. A dimer is identified for 2, which is shown to be a product of the experiment and not present in the parent material. In addition, a 1:1 adduct with NH₄ ⁺ is identified for 4 and 11 where the NH₄ ⁺ originates from the acid hydrolysis of acetonitrile. Finally, a highly unique ion, Pt⁺, a bare platinum ion, is observed in all COD complexes indicating that a radical mechanism must accompany the decomposition of the COD complexes during the fragmentation process.     

Preparation and properties of [PtII(SS)(NN)]-type complexes and their iodine-doped analogues

Summary Complexes of the general formula [Pt(SS) (NN)], where SS is dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate) or pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate) and NN is bipy (2,2-bipyridine) or phen (1,10-phenanthroline), were prepared by the reaction of [PtCl₂(NN)] with dithiolate ligands. The¹H-n.m.r. spectra shows upfield shifts in the bipy or phen signals upon substitution of the chlorides in [PtCl₂(bipy)] or [PtCl₂(phen)] by dddt or pddt. The u.v.-vis. spectra exhibits intense intramolecular ligand-to-ligand charge transfer bands ca. 600 nm. Cyclic voltammograms show a reversible oxidation step, assigned to [Pt(SS) (NN)]⁰/[Pt(SS)(NN)]⁺. When the complexes were partially oxidized by I₂, two broad e.s.r. signals atg = 1.91,g = 2.02 appeared. Raman spectra show the presence of I ₃ ^– and I^5/– in the iodine-doped complexes. The electrical conductivities of the neutral mixed ligand complexes (10^–9-10^–10S cm^–1) are raised to 10^–7–10^–8S cm^–1 by I₂ doping.     

Zur Koordinationschemie des 1,3-Thiaselenol-2-thion-4,5-dithiolats (dmits) – ein Vergleich mit 1,3-Dithiol-2-thion-4,5-dithiolat (dmit)

Coordination Chemistry of 1,3-Thiaselenole-2-thione-4,5-dithiolate (dmits) – Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III)-bis-chelates of 1,3-thiaselenole-2-thione-4,5-dithiolate (dmits) of the general type (Bu₄N)_n[M(dmits)₂] (n = 2: M = Zn, Cd, Hg, Ni, Cu, Pd; n = 1: M = Au, Ni) are described. By comparison of the i.r., ¹³C-n.m.r., epr spectra and cyclovoltammetric data of chelates of dmits and those of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of the substitution of selenium for sulfur on position 3 of the heterocyclic ligand dmit are discussed.     

Zur Koordinationschemie des 1,3-Dithiol-2-thion-4,5-diselenolats (dsit) – ein Vergleich mit 1,3-Dithiol-2-thion-4,5-dithiolat (dmit)

Coordination Chemistry of 1,3-Dithiole-2-thione-4,5-diselenolate (dsit) — Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III) bis-chelates of 1,3-dithiole-2-thione-4,5-diselenolate (dsit) of general type (Bu₄N)_n[M(dsit)₂] (n = 2: M ? Zn, Cd, Hg, Cu, Ni, Pd, Pt; n = 1: M ? Ni, Au) are described. By comparison of the ir, ¹³C nmr, epr spectra, cyclovoltammetric data, and x-ray investigations (nickel-bis-chelates) of chelates of dsit and those of the chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of selenium for sulfur substitution on position 4 and 5 of the heterocyclic ligand are discussed.     

The decomposition kinetics of [Et4N]2[M(dmit)2] (M = Ni, Pd) in a nitrogen atmosphere using thermogravimetry

Thermal properties and thermal decompositions of [NEt₄]₂[M(dmit)₂] (M = Ni(II), Pd(II), dmit = 1,3-dithiole-2-thione-4,5-dithiolate) have been studied by thermogravimetry (TG). The TG analysis has shown that the complexes are thermally stable up to 460 K and the decomposition of the complexes occurs in three consecutive stages up to 873 K. A thermal stability scale for [M(dmit)₂]ⁿ⁻ anions was based on the thermal properties. Kinetics parameters, such as activation energy, E_a, and kinetic apparent pre-exponential factor, ln A_app, have been calculated from the thermogravimetric data at heating rates of 10, 15, 20 and 25 K/min involving differential (Friedman's equation) and integral (Flynn-Wall-Ozawa's equation) methods.     

Synthese und Eigenschaften von molekularen Leitern auf der Basis von dmit-isologen Chelaten Kristall- und Molekülstruktur des Tetramethylammonium-bis-[bis-(1,3-dithiol-2-selon-4,5-diselenolato)nickelat]; [(CH3)4N][Ni(dsise)2]2

Syntheses and Properties of Molecular Conductors based on dmit isologous Chelates. Crystal and Molecular Structure of Tetramethylammonium-bis-[bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate]; [(CH₃)₄N] [Ni(dsise)₂]₂ Syntheses and properties of dichalcogenolate chelates of the general type [(CH₃)₄N]_n[ML₂] (n ≤ 2; M = Ni, Pd, Pt); L = dmit (1,3-dithiole-2-thione-4,5-dithiolate), dmise (1, 3-dithiole-2-selone-4,5-dithiolate), dsit (1, 3-dithiole-2-thione-4,5-diselenolate), dsise (1, 3-dithiole-2-selone-4,5-diselenolate), dsis (1, 3-diselenole-2-selone-4,5-diselenolate) are reported. The effects of the chalcogen atom variation in these chelates are discussed by using UV/VIS, IR, EPR, cyclovoltammetric and conductivity data. The x-ray structure of [(CH₃)₄N][Ni(dsise)₂]₂ (space group Pccn, a = 7.427(1), b = 39.144(5), c = 11.836(1) Å) and the conductivity of the crystal (12 S cm^?1 at room temperature) are given.     

A New Paramagnetic Pd(dmit)2 Salt: Tris(2,2′-Bipyridine)Nickel(II) Bis(1,3-Dithiole-2-Thione-4,5-Dithiolato)Palladate(II) Mono-Acetonitrile; [Ni(bpy)3][Pd(dmit)2]·CH3CN

Combination of the [Ni(bpy)₃]²⁺ cation complex and the [Pd(dmit)₂]⁻ anion (dmit=C₃S₅²⁻=1,3-dithiole-2thione-4,5-dithiolate) has resulted in the paramagnetic [Ni(bpy)₃][Pd(dmit)₂]·CH₃CN compound, a suitable precursor for a molecular magnetic conductor. Its crystal structure consists of a Pd(dmit)₂ anion arrangement that is quite different from segregated stack layers often found for M(dmit)₂−based compounds. The reduction of the [Pd(dmit)₂]^- to the 2− charged anion in the title compound most probably is the result of a charge disproportionation between Pd(dmit)₂ anions.     

Synthesis,structure and physical properties of nickel bis(dithiolene) complexes with different cations

A series of new complexes of multi-sulfur 1,2-dithiolene ligands, [Ru(bipy)₃][Ni(L)₂]₂ (bipy?=?2,2′-bipyridine; L?=?pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate), dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate)), have been synthesized and characterized. One typical complex, [Ru(bipy)₃][Ni(pddt)₂]₂·2H₂O (1), crystallized in an acentric space group of P2₁2₁2₁, with the cell dimensions of a?=?8.634(1), b?=?14.560(1), c?=?49.889(5)?Å, α?=?β?=?γ?=?90°, and Z?=?4. It consists of alternating columns of cations and anions along the a direction. The structure was refined by full matrix least squares methods to R ₁?=?0.0340, wR ₂?=?0.0670. Magnetic studies on [Ph₂Cr][Ni(dddt)₂] are also reported.     

Two Polymorphs of (Anilinium)(18-Crown-6)[Ni(dmit)2]: Structure and Magnetic Properties

Two polymorphs of monovalent [Ni(dmit)₂]⁻ (dmit²⁻=2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)₂], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)₂]⁻ molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)₂], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ=190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)₂]⁻ dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)₂]⁻ arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K.     

Synthesis, structure, and electroconductivity of new radical cation salt [Pd(dddt)2]2GaBr4

A new radical cation salt based on the dithiolate complex Pd(dddt)₂ (dddt=5,6-dihydro-1,4-dithiine-2,3-dithiolate) with the tetrahedral anion [GaBr₄]^? was synthesized. The crystal and molecular structure was determined by XRD analysis. The crystal structure of the salt contains Pd(dddt)₂ cation layers alternating with layers of [GaBr₄]^? anions along thec axis of the unit cell. The cation layers contain stacks of Pd(dddt)₂, with a Pd...Pd distance of 3.011 Å. The electroconductivity of [Pd(dddt)₂]₂GaBr₄, single crystals at room temperature is 0.25 Ohm^?1 cm^?1 and decreases with temperature decrease, the activation energy beingE _a=0.66 eV.     

Synthesis,characterization, X-ray structure and preliminary in vitro antitumor activity of the nitrosyl complex fac-[RuCl3(NO)(dppf)], dppf = 1,1′-bis(diphenylphosphine)ferrocene

The reaction of RuCl₃NO · 2H₂O with stoichiometric amount of dppf, 1,1′-bis(diphenylphosphino)ferrocene, afforded the new neutral nitrosyl complex fac-[RuCl₃(NO)(dppf)] which was characterized by spectroscopical, electrochemical and X-ray crystallography techniques as well as elemental analysis. The ν_NO band in the IR spectrum is at 1860 cm⁻¹ (CH₂Cl₂ solution) and in the cyclic voltammogram an irreversible wave was observed at −1.35 V, both are characteristics of a nitrosonium (NO⁺) character for the coordinated NO. Additionally, preliminary in vitro antitumor activity against the MDA-MB-231 breast tumor cell line was carried out for the new complex. The initial results indicated an important activity for fac-[RuCl₃(NO)(dppf)] (IC₅₀ = 10 ± 3 μM ). The complex has a higher cytotoxicity than the precursor complex RuCl₃NO · 2H₂O, the free dppf ligand as well as the reference metallodrug cisplatin.     

Electrical conductivities of bis(1,3-dithiole-2-thione-4,5-dithiolato)rhodate anion salts

RhCl₃·3H₂O reacted with Na₂dmit (dmit²⁻; 1,3-dithiole-2-thione-4,5-dithiolate anion) and [NBu₄ⁿOH in methanol to afford [NBu₄ⁿ][Rh(dmit)₂] (1) and [NBu₄ⁿ]_1.5[Rh(dmit)₂] (2). Salt 1 was oxidized electrochemically in acetonitrile to afford [NBu₄ⁿ]_0.4[Rh(dmit)₂] (3). Suspended powders of 1 or 2 reacted with iodine in hexane to afford [NBu₄ⁿ][Rh(dmit)₂][I₃]_1.3 (4) or [NBu₄ⁿ]_1.5[Rh(dmit)₂[I₃]_0.4 (5). On the other hand, 1 dissolved in acetonitrile, reacted with bromine and iodine to yield [NBu₄ⁿ]_0.25[Rh(dmit)₂Br] (6) and [NBu₄ⁿ]_0.35[Rh(dmit)₂I] (7), respectively. All the salts behave as semi-conductors with electrical conductivities of 1 x (10⁻⁵ − 10⁻⁸) S cm⁻¹ at 25°C measured for compacted pellets. Electronic absorption, ESR and X-ray photoelectron spectra of the salts are discussed.     

SYNTHESES AND CRYSTAL STRUCTURES OF ISOMALONONITRILE DITHIOLATO COMPLEXES (Bu4N)2Zn(i-mnt)2 AND (Et4N)2Pd(i-mnt)2

Abstract

Two isomalononitrile dithiolato complexes, (Bu₄N)₂Zn(i-mnt)₂ (1) and (Et₄N)₂Pd(i-mnt)₂ (2) were synthesized and characterized by elemental analysis, IR and electronic spectroscopy. Their structures have been crystallographically determined. The reaction of (Et₄N)₂Pd(i-mnt)₂ (2) with (Et₄N)₂WS₄ gives (Et₄N)₂WS₄Pd(i-mnt).     

Synthesis and properties of [Pt(4-CO2CH3-py)2(dmit)] and [Pt(4-NO2-py)2(mnt)]: Exploring tunable Pt dyes

Two [Pt(II)(substituted-pyridyl)₂(dithiolate)] dyes with the formulas [Pt(4-CO₂CH₃-py)₂(dmit)] and [Pt(4-NO₂-py)₂(mnt)] (where py = pyridyl, dmit = 1,3-dithiol-2-thione-4,5-dithiolate and mnt = maleonitriledithiolate) and their dichloride precursors [PtCl₂(4-R-py)₂] have been synthesized and compared to a previously-reported dye [Pt(4-CO₂CH₃-py)₂(mnt)]. Variation of either the pyridyl ligands or the ditholate ligand showed tuning of the electrochemical and spectroscopic characteristics of the dyes as evidenced by cyclic and differential pulse voltammetry, hybrid DFT calculations, UV/Vis spectroelectrochemistry and in situ EPR spectroelectrochemistry. The HOMO was shown to be mostly dithiolate based and the LUMO pyridyl based allowing absorption characteristics to be predictably tuned to longer wavelengths, which is important for optimization of such dyes in applications such as solar energy conversion.     

Crystal structure and EPR spectra of (Bu<Subscript>4</Subscript>N)<Subscript>2</Subscript>[V(dmit)<Subscript>3</Subscript>]

The tris-chelate complex of vanadium(IV) (Bu₄N)₂[V(dmit)₃] is prepared from VCl₃ and (Bu₄N)₂[Zn(dmit)₂] (dmit = isotrithionedithiolate C₃S₅ ^2–) and characterized by single crystal XRD and mass spectrometry. The complex crystallizes in the space group Pna2₁ and has a distorted octahedral environment of vanadium. The complex is paramagnetic and gives a characteristic EPR spectrum in both solution and solid phase. The g factors and hyperfine interaction constants are determined.     

Synthesis,X-ray crystal structure and electrochemical properties of (dithiolato)(diimine)copper(II) complexes: [Cu(mnt)(phen)] n and [Cu(dmit)(phen)] 2

Copper (II) complexes [Cu(dmit)(phen)]₂ (1) and [Cu(mnt)(phen)] _n (2) (mnt^2??=?maleonitriledithiolate, dmit^2??=?1,3-dithiole-2-thione-4,5-dithiolate, phen?=?1,10-phenanthroline) have been prepared by ligand-exchange between phen and [N(Bu)₄]₂[Cu(dmit)₂] or [N(Bu)₄]₂[Cu(mnt)₂]. Both complexes have been characterized by spectroscopic, electrochemical, and single-crystal X-ray analysis. In complex 1, dimers are extended into a two-dimensional array by weak S5–Cu contacts. In complex 2, monomers are extended into chains in a head-to-tail arrangement by weak Cu–S coordination bonds and π–π stacking interactions.